CN105504284B - A kind of polymer containing quaternary ammonium group, anion-exchange membrane and preparation method thereof - Google Patents

A kind of polymer containing quaternary ammonium group, anion-exchange membrane and preparation method thereof Download PDF

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CN105504284B
CN105504284B CN201610004095.3A CN201610004095A CN105504284B CN 105504284 B CN105504284 B CN 105504284B CN 201610004095 A CN201610004095 A CN 201610004095A CN 105504284 B CN105504284 B CN 105504284B
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tertiary amine
side chain
polymer
amine group
chloropropyls
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CN201610004095.3A
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CN105504284A (en
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郑吉富
张所波
李胜海
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中国科学院长春应用化学研究所
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20Polysulfones
    • C08G75/23Polyethersulfones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48Polymers modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2371/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2381/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06Polysulfones; Polyethersulfones

Abstract

The invention provides a kind of polymer containing quaternary ammonium group, is obtained after being reacted by the polymer that side chain contains tertiary amine group with quaternizing agent;The polymer that the side chain contains tertiary amine group contains the one or more in tertiary amine group poly (aryl ether sulfone ketone) for side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine group PAEK and side chain;The quaternizing agent is the one or more in iodomethane, (3 chloropropyl) trimethoxy silane and (3 chloropropyl) trimethoxy silane system.The present invention uses polyether sulphone of the side chain containing tertiary amine, PAEK or poly (aryl ether sulfone ketone) as raw material, grafting produces quaternary ammonium group under appropriate conditions, and between siloxane group and quaternary ammonium group it is present in a manner of covalent bond is bonded in new anion-exchange membrane material structure, and then be advantageous to the alkaline stability of membrane material and the raising of dimensional stability, while the toughness and mechanical performance of such membrane material can also be improved.

Description

A kind of polymer containing quaternary ammonium group, anion-exchange membrane and preparation method thereof

Technical field

The present invention relates to charged technical field of membrane, and in particular to a kind of polymer containing quaternary ammonium group, anion exchange Film and preparation method thereof.

Background technology

Anion-exchange membrane (Anion Exchange Membrane, abbreviation AEM), it is that a kind of selectivity passes through anion The polymer dielectric film of (generally only allowing hydroxide ion to pass through), it contains basic activated group, has choosing to anion Select permeability.Anion-exchange membrane is made up of three parts:Main polymer chain with fixed group is macromolecule matrix (also referred to as base Film), the anion that can move freely on the active group (i.e. cation) and active group of lotus positive electricity.Anion is evaluated to hand over Two important indexs for changing film properties are exactly ionic conductivity and alkaline stability (or chemical stability), and ionic conductivity is usual Weighed using ionic conductivity, its value is higher, and film conductive capability is bigger.Alkaline stability refers to membrane material institute in the basic conditions Embody the stability of ionic group or polymer backbone structure.The characterization method of generally use has:The ionic conductivity of film with The change of time;The change of nuclear magnetic spectrogram intermediate ion group (or polymer backbone structure) chemical shift.In addition, in NF membrane skill Art field, on the premise of requiring that film has satisfactory electrical conductivity, solvent resistant NF membrane also turns into the research in the field in recent years Focus, solvent resistant refer to membrane material under organic solvent existence condition, the insoluble characteristic embodied.

Anion-exchange membrane has very extensive application, and it is in separator, purifying plant and electrochemical assembly Important component, in fields such as chlorine industry, water treatment industry, heavy metal recovery, hydrometallurgy and electrochemical industries All play very important effect.In recent years, towards country to the great demand of energy field and the great market of electronic product, The research of fuel cell, energy-storage battery and electrokinetic cell etc. turns into the important directions of electrochmical power source development in recent years, its In, fuel cell is considered as the electrical source of power of new generation that clean energy resource field adapts to future source of energy and environmental requirement.Particularly Alkaline polymer electrolyte membrane (AEMs) fuel cell can break away from the dependence to precious metals pt, using stabilization, cheap and easy to get Transition-metals and their oxides as elctro-catalyst, so as to show wide actual application prospect.

For example existing DMFC is mainly concentrated in keeping the ionic conduction of film with AEMs research Its chemical stability is improved while rate, mechanical strength and alcohol-rejecting ability etc. common practice mainly have:1) ion is optimized Unit structure is with being distributed and improving the ion exchange capacity of AEMs materials;2) work quickening electricity under temperature conditionss as high as possible Pole reaction speed, to make up the inferior position on alkaline membrane conductivity.But improving ion exchange capacity often makes polymer film excessive Hydrophilic, the mechanical performance of film significantly declines.After operating temperature is improved, polymer film even can dissolve or degrade in water, The application requirement of electrochemical device can not be met.3) inorganic nano material (silica, heteropoly acid etc.) or poroid polymerization are utilized Thing is modified processing (blending, doping, crosslinking, hole filling) to polyelectrolyte, has in heat endurance and crossover of methanol etc. It is obvious progressive.But because the doping of inorganic nano material normally results in the reduction of the ionic conductance of AEMs materials, because Most dopant has poor ionic conductivity or does not have ionic conductivity at all, while this kind of dopant is in polymer The conduction of ion is hindered in dielectric film to a certain extent.In addition, these dopants frequently can lead to film microstructure (sky Cave, interfacial separation) change, cause the reduction of film toughness and machining property, can also enable contact of the film with catalyst layer Power weakens, it is impossible to meets the needs of electrochemical device long-time stability.

Therefore, exploratory development prepares good chemical stability and disclosure satisfy that the high-performance AEMs materials of electrochemical applications, Prepare suitable AEMs fuel cells practical application, commercialized anion exchange membrane material be very necessary.

The content of the invention

In view of this, the technical problem to be solved in the present invention be to provide a kind of polymer containing quaternary ammonium group, it is cloudy from Proton exchange and preparation method thereof, anion-exchange membrane provided by the invention, there is the stability of higher membrane material, toughness and machine Tool performance.Meanwhile the present invention prepares cross-linking type anion exchange membrane material, film forming and cross-linking process collection using film-forming process in situ In one, the process of film is enormously simplify, it is achieved thereby that homogenization and long term stabilization prepared by such material batch, easily In large-scale production.

In view of this, the invention provides a kind of polymer containing quaternary ammonium group, the poly- of tertiary amine group is contained by side chain Compound obtains after being reacted with quaternizing agent;

The polymer that the side chain contains tertiary amine group is side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine The PAEK and side chain of group contain the one or more in tertiary amine group poly (aryl ether sulfone ketone);

The quaternizing agent is iodomethane, (3- chloropropyls) trimethoxy silane and (3- chloropropyls) trimethoxy silane One or more in system.

Preferably, described (3- chloropropyls) trimethoxy silane system is (3- chloropropyls) trimethoxy silane and iodo Thing;The iodo thing is anhydrous sodium iodide and/or anhydrous KI.

Preferably, the side chain contains in the polymer of tertiary amine group, passes through alkyl between the tertiary amine group and main chain Group is connected;

The alkyl group includes-CH2-、-CH2CH2-、-CH2CH2CH2- and-CH2(CH2)4CH2- in one kind or more Kind.

Present invention also offers a kind of preparation method of anion-exchange membrane, comprise the following steps,

A) under protective atmosphere, side chain is contained to the non-matter of polymer, quaternizing agent and dry polar of tertiary amine group After sub- solvent hybrid reaction, the polymer solution containing quaternary ammonium group is obtained;

The polymer that the side chain contains tertiary amine group is side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine The PAEK and side chain of group contain the one or more in tertiary amine group poly (aryl ether sulfone ketone);The quaternizing agent is iodine first One or more in alkane, (3- chloropropyls) trimethoxy silane and (3- chloropropyls) trimethoxy silane system;

B alcohols solvent) is added in the polymer solution containing quaternary ammonium group obtained to above-mentioned steps and carries out partial hydrolysis After reaction, casting solution is obtained;

C the casting solution for) obtaining above-mentioned steps carries out casting film, while after carrying out self-crosslinking process, obtains anion Exchange membrane.

Preferably, described (3- chloropropyls) trimethoxy silane system is (3- chloropropyls) trimethoxy silane and iodo Thing;The iodo thing is anhydrous sodium iodide and/or anhydrous KI.

Preferably, the molal quantity of the quaternizing agent contains in the polymer of tertiary amine group less than or equal to the side chain The molal quantity of tertiary amine group.

Preferably, the temperature of the reaction is 60~100 DEG C, and the time of the reaction is 18~48 hours.

Preferably, the reaction dissolvent is anhydrous polar aprotic solvent.

Preferably, the time control of the partial hydrolysis reaction is dense less than critical gel in polymer solution gel strength Degree.

Preferably, the temperature of the self-crosslinking process is 50~70 DEG C, and the time of the self-crosslinking process is 8~12h.

The invention provides a kind of polymer containing quaternary ammonium group, the polymer and quaternary ammonium of tertiary amine group are contained by side chain Obtained after changing reagent reacting;The polymer that the side chain contains tertiary amine group is that side chain contains the polyether sulphone of tertiary amine group, side PAEK and side chain that chain contains tertiary amine group contain the one or more in tertiary amine group poly (aryl ether sulfone ketone);It is described quaternized Reagent is one kind or more in iodomethane, (3- chloropropyls) trimethoxy silane and (3- chloropropyls) trimethoxy silane system Kind.Compared with prior art, the present invention uses polyether sulphone of the side chain containing tertiary amine, PAEK or poly (aryl ether sulfone ketone) as raw material, Grafting produces quaternary ammonium group under appropriate conditions, and is in a manner of covalent bond is bonded between siloxane group and quaternary ammonium group It is present in new anion-exchange membrane material structure, and then is advantageous to the alkaline stability of membrane material and proposing for dimensional stability Height, while the toughness and mechanical performance of such membrane material can also be improved.Test result indicates that cross-linking type prepared by the present invention is cloudy Ion exchange membrane material, ionic conductivity 0.043S cm at its 60 DEG C-1, the ionic conductivity after alkali process (10 days) is 0.040, in solvent resistance test, insoluble in DMAc, DMSO and NMP, rate of weight loss is respectively less than 5%.

Brief description of the drawings

Fig. 1 is anion-exchange membrane 1P of the present invention1And 1P2Structure and polymeric quartenary ammonium procedure chart;

Fig. 2 is polymer 1P in the present invention0(left side) and cross-linked polymer 1P2The photoelectron spectroscopy compares figure on (right side);

Fig. 3 is cross-linked polymer 1P in the present invention2Solid23Si NMR spectras;

Fig. 4 is polymer 1P in the present invention1With cross-linked polymer 1P2INFRARED SPECTRUM compares figure;

Fig. 5 is cross-linked polymer 1P under room temperature condition2(60 days) are soaked in DMAc (a), DMSO (b) and NMP (c) Pictorial diagram;

Fig. 6 is linear polymer 1P in the present invention1With cross-linked polymer 1P2Alkaline stability compares figure;

Fig. 7 is that solid state nmr tests cross-linked polymer 1P2Alkaline stability figure;

Fig. 8 is linear polymer 1P1With cross-linked polymer 1P2Ionic conductivity changes compares figure after alkali process.

Embodiment

For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.

All raw materials of the present invention, its source is not particularly limited, commercially buying or according to people in the art Known to member prepared by conventional method.

All raw materials of the present invention, its purity is not particularly limited, pure present invention preferably employs analyzing.

The invention provides a kind of polymer containing quaternary ammonium group, the polymer and quaternary ammonium of tertiary amine group are contained by side chain Obtained after changing reagent reacting;The polymer that the side chain contains tertiary amine group is that side chain contains the polyether sulphone of tertiary amine group, side PAEK and side chain that chain contains tertiary amine group contain the one or more in tertiary amine group poly (aryl ether sulfone ketone);It is described quaternized Reagent is one kind or more in iodomethane, (3- chloropropyls) trimethoxy silane and (3- chloropropyls) trimethoxy silane system Kind.

Quaternizing agent of the present invention is preferably iodomethane, (3- chloropropyls) trimethoxy silane and (3- chloropropyls) three One or more in methoxy silane system, more preferably (3- chloropropyls) trimethoxy silane or (3- chloropropyls) trimethoxy Base silane system, it is most preferably (3- chloropropyls) trimethoxy silane system;(3- chloropropyls) the trimethoxy silane system Preferably (3- chloropropyls) trimethoxy silane and iodo thing, the iodo thing are preferably anhydrous sodium iodide and/or anhydrous iodate Potassium, more preferably anhydrous KI.

The present invention is especially limited without other the polyether sulphone containing tertiary amine group, ripe with those skilled in the art The polyether sulphone known;The present invention is especially limited without other the PAEK containing tertiary amine group, with this area PAEK known to technical staff;The present invention is especially limited without other the poly (aryl ether sulfone ketone) containing tertiary amine group System, with poly (aryl ether sulfone ketone) well known to those skilled in the art or polyether sulphone (ketone).The present invention contains uncle to the side chain The polymer of amine groups is especially limited without other, and the polyarylether of tertiary amine group is contained with side chain well known to those skilled in the art PAEK and side chain that sulfone, side chain contain tertiary amine group contain the one or more in tertiary amine group poly (aryl ether sulfone ketone), Tertiary amine comonomer includes in the more preferably above-mentioned polymer architecture of the present invention:Biphenyl type tertiary amine, diphenyl ether type tertiary amine and phenolphthalein type One or more in tertiary amine.

The present invention between tertiary amine group and main chain by alkyl group it is also preferred that be connected;The alkyl group is preferred Including-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2(CH2)4CH2-.The present invention to the tertiary amine group polymer monomer Number is not particularly limited in structure (polymer repeated fragment), and the present invention is preferably 1~2, i.e., tertiary amine group is in monomer knot There are single functionality and/or the class of bifunctionality two in structure.

The present invention uses the polymer such as the polyether sulphone that side chain contains tertiary amine group, poly aryl ether ketone as raw material, anhydrous Under the iodo thing existence condition of catalytic amount, iodomethane or (3- chloropropyls) trimethoxy silane (CPTMS) and tertiary amine are utilized Radical reaction generates quaternary ammonium group, and quaternary ammonium group is connected by alkyl chain with main polymer chain and siloxane group respectively, wherein It is to exist in a manner of covalent bond is bonded between siloxane group and quaternary ammonium group.This structure and bonded mode effectively avoid Due to being doped with poor ionic conductivity or the basic inorganic nano material without ionic conductivity, so as to causing The ionic conductance of AEMs materials reduces the problem of serious;Also these dopants are solved and frequently can lead to film microstructure (sky Cave, interfacial separation) change, cause the reduction of film toughness and machining property.

Present invention also offers a kind of preparation method of anion-exchange membrane, comprise the following steps,

A) under protective atmosphere, side chain is contained to the non-matter of polymer, quaternizing agent and dry polar of tertiary amine group After sub- solvent hybrid reaction, the polymer solution containing quaternary ammonium group is obtained;

The polymer that the side chain contains tertiary amine group is side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine The PAEK and side chain of group contain the one or more in tertiary amine group poly (aryl ether sulfone ketone);The quaternizing agent is iodine first One or more in alkane, (3- chloropropyls) trimethoxy silane and (3- chloropropyls) trimethoxy silane system;

B alcohols solvent) is added in the polymer solution containing quaternary ammonium group obtained to above-mentioned steps and carries out partial hydrolysis After reaction, casting solution is obtained;

C the casting solution for) obtaining above-mentioned steps carries out casting film, while after carrying out self-crosslinking process, obtains anion Exchange membrane.

The present invention contains the polymer of tertiary amine group, quaternizing agent and anhydrous first under protective atmosphere, by side chain After polar non-solute hybrid reaction, the polymer solution containing quaternary ammonium group is obtained;The side chain contains tertiary amine group Polymer contains tertiary amine groups for the PAEK and side chain that side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine group One or more in group's poly (aryl ether sulfone ketone);The quaternizing agent is iodomethane, (3- chloropropyls) trimethoxy silane and (3- Chloropropyl) one or more in trimethoxy silane system.

In the optimum principles and the foregoing polymer containing quaternary ammonium group such as selection and structure of the present invention to the raw material Consistent, this is no longer going to repeat them.

The present invention is especially limited without other the protective atmosphere, with protectiveness gas well known to those skilled in the art Atmosphere, the present invention are preferably nitrogen or inert gas, more preferably nitrogen;The present invention is to the anhydrous polar aprotic solvent Especially limited without other, with anhydrous polar aprotic solvent well known to those skilled in the art, the present invention is preferably DMF, DMA, DMSO or DMAc, more preferably DMAc;The present invention is especially limited without other the condition of the hybrid reaction, with The condition of the similar reaction of this area skill, the temperature of reaction of the present invention is preferably 60~100 DEG C, more preferably 70~95 DEG C, more preferably 75~90 DEG C, most preferably 85 DEG C;The time of the reaction is preferably 18~48 hours, more preferably 20~ 40 hours, more preferably 22~35 hours, most preferably 24~32 hours.

The additional proportion for the polymer that the present invention contains tertiary amine group to the quaternizing agent and side chain does not limit especially System, those skilled in the art can be adjusted and select according to actual conditions, product requirement and performance requirement, of the present invention The mol ratio for the polymer that quaternizing agent and side chain contain tertiary amine group determines the graft ratio of quaternization process, the quaternary ammonium Specifically depending on the number of tertiary amine group in polymer repeated fragment, molal quantity should be less than being equal to tertiary amine group the dosage of change reagent Molal quantity.The preferably quaternizing agent molal quantity of the invention is less than or equal to the polymer that the side chain contains tertiary amine group The molal quantity of middle tertiary amine group, more preferably described quaternizing agent molal quantity are equal to the polymer that the side chain contains tertiary amine group The molal quantity of middle tertiary amine group.The present invention contains the addition sequence of the polymer of tertiary amine group to the quaternizing agent and side chain It is not particularly limited, with addition sequence well known to those skilled in the art, side chain is preferably first contained tertiary amine groups by the present invention The polymer of group is dissolved in anhydrous polar aprotic solvent, polymer solution is configured to, after dissolving completely to be mixed, to system Middle addition quaternizing agent;The solid content of the polymer solution is preferably 5wt%~10wt%, and more preferably 6wt%~ 9wt%, most preferably 7wt%~8wt%;The present invention is when selecting a variety of quaternizing agents, the present invention preferably iodomethane It is eventually adding.The present invention is when quaternizing agent is (3- chloropropyls) trimethoxy silane (CPTMS) and anhydrous iodo thing, this hair The bright ratio to the two is not particularly limited, and those skilled in the art can be according to actual conditions, product requirement and performance requirement It is adjusted, the present invention is preferably the anhydrous iodo thing of catalytic amount.

For ease of understanding, the reaction raw materials are specifically described spy the present invention, skilled artisans appreciate that Technical scheme disclosed in this invention not is only limited to the following specifically describes.

As reacted shown in formula (I),

Wherein, the polymer that side chain contains tertiary amine group is preferably the polymer that short-side chain contains tertiary amine group, Mei Gechong Contain di-tertiary amine group in multiple unit;X is CH3I's is actually added into molal quantity, and y is actually added into molal quantity for CPTMS's, and z is uncle Amine groups are actually added into molal quantity, x+y=z, 0.5z≤y≤z;When the amount of being actually added into is unit equivalent, z=2n, 0 < n ≤1;

Wherein, the formula (2) in formula (I) is reacted, i.e., the polymer that short-side chain contains tertiary amine group preferably is selected from formula (3) or formula (4),

Wherein, Ar preferably is selected from formula (5)~formula (7),

Wherein, Ar`` preferably is selected from formula (8)~formula (12)

As reacted shown in formula (II),

Wherein, the polymer that side chain contains tertiary amine group is preferably the polymer that long side chain contains tertiary amine group;X is CH3I Be actually added into molal quantity, the molal quantity that is actually added into that y is CPTMS, z is the molal quantity that is actually added into of tertiary amine group, x+y=z, 0.5z≤y≤z, m=0,1 or 4;When the amount of being actually added into is unit equivalent, z=n, 0 < n≤1;

Wherein, Ar's and Ar`` is specific preferably identical with above-mentioned optimum principle;

Wherein, react formula (II) in formula (13), i.e., the polymer that long side chain contains tertiary amine group preferably be selected from formula (14)~ Formula (16)

Counter ion counterionsl gegenions OH is eliminated in the above-mentioned reaction equation of the present invention-

The polymer solution containing quaternary ammonium group of the invention after above-mentioned steps, obtained, then directly adds thereto After entering alcohols solvent progress partial hydrolysis reaction, casting solution is obtained.

The alcohols solvent is not particularly limited the present invention, with alcohols solvent well known to those skilled in the art, The present invention is preferably the one or more in 95% ethanol, ethanol, methanol and isopropanol, more preferably 95% ethanol, first In alcohol and isopropanol, most preferably 95% ethanol.The additional proportion of the neutralized alcohol is not particularly limited the present invention, ability Field technique personnel can be adjusted according to actual conditions, and the present invention is preferably 3%~10%, more preferably 4%~8%, more Preferably 5%~6%, most preferably 5%;The present invention is preferably 6~8 to the pH value of partial hydrolysis reaction, more preferably 7;The present invention to the partial hydrolysis reaction time be not particularly limited, those skilled in the art can according to actual conditions, Product requirement or performance requirement are adjusted, and the present invention is preferably to reach critical gel strength in polymer solution gel strength C Terminate reaction, more preferably 10~120 minutes, more preferably 15 before (critical gelation concentration, Cg) ~90 minutes, more preferably 30~60 minutes, most preferably 30 minutes.

The present invention controls siloxane moieties hydrolysis after the completion of grafting directly under alcohols solvent existence condition, makes silicon Oxyalkyl group produces crosslinkable Si-OH groups, and when the content of Si-OH groups in polymer solution gradually increases, system is coagulated Gum concentration C gradually increases, and also forms Si-O-Si the or Si-O-Si-OH cross-linked networks of nascent state, while alcohols solvent (neutrality) Under existence condition, it can control and suppress the formation speed of the Si-O-Si or Si-O-Si-OH cross-linked networks of nascent state.If adopt The speed generated with acid (hydrochloric acid solution) or alkaline (ammoniacal liquor) hydrolysis Si-OH groups, is unfavorable for Si-O-Si cross-linked networks Formation.The present invention is by the control and the control of hydrolysis time to system acid-base property, to realize the control to system gel strength C System.Critical gel strength (critical gelation concentration, Cg) is reached in polymer solution gel strength C Before, carry out the paved of subsequent film.

The casting solution that the present invention obtains above-mentioned steps carries out casting film, while after carrying out self-crosslinking process, obtains the moon Amberplex.

The casting film is not particularly limited the present invention, is in a manner of casting film well known to those skilled in the art Can, the present invention is preferably casting film-forming on a glass;The equipment of the casting film is not particularly limited the present invention, with this The equipment of casting film known to art personnel, the present invention are preferably casting film machine.The present invention is to the selfing The condition of connection process is not particularly limited, and with self-crosslinking condition well known to those skilled in the art, the present invention is preferably certainly The temperature of crosslinking is 50~80 DEG C, more preferably 60~70 DEG C;The time of the crosslinking is preferably 8~12h, more preferably 9~ 11h。

Membrane material obtained above is preferably also dried in vacuo by the present invention, ion exchange and cleaning step.The present invention Vacuum drying actual conditions is not particularly limited, with drying condition well known to those skilled in the art, institute of the present invention It is preferably 100~150 DEG C to state drying temperature, more preferably 110~140 DEG C, most preferably 120~130 DEG C;The drying time Preferably 12~24h, more preferably 15~20h, most preferably 17~18h.The present invention does not have to the actual conditions of ion exchange Especially limitation, with ion-exchange method well known to those skilled in the art, present invention preferably employs molten in 1M sodium hydroxides 40~55h is soaked in liquid and carries out ion exchange.The concrete mode of cleaning is not particularly limited the present invention, with people in the art The cleaning way of anion-exchange membrane known to member, the present invention is preferably to soak 40~55h with deionized water, and is repeated 3~5 times.The thickness of anion-exchange membrane of the present invention is preferably 35~60 μm, more preferably 40~55 μm.

Anion-exchange membrane has been prepared by above-mentioned steps in the present invention, and invention uses self assembly-selfing The new strategy of connection, original position prepare the inorganic-organic hybrid anion exchange membrane material of cross-linking type (Si-O-Si), its design feature It is to be present in new anion exchange membrane material in a manner of covalent bond is bonded between alkylsiloxane group and quaternary ammonium group to be Material.On the one hand, siloxane group and quaternary ammonium group are bonded with covalent bond, can solve well because doping (or blending) is inorganic Hole and interfacial separation problem caused by nano material, and then be the toughness and machining property for improving such membrane material Energy.On the other hand, by the acid-base property and hydrolysis degree of control system, Si-O-Si cross-linked network is formed in film forming procedure in situ Network structure, film forming are integrated in one with cross-linking process, enormously simplify film-forming process.This method is a kind of raising anion-exchange membrane Material alkaline stability and solvent-proof effective ways, while also have significantly in the heat endurance of film and dimensional stability etc. Improve.

The anion-exchange membrane that the present invention is prepared to above-mentioned steps carries out alkali stability experiment and solvent resistance respectively Test.

Wherein, soaked within (10 days) for a long time with 1M NaOH solutions under the conditions of the alkali stability of film mainly passes through 60 DEG C Afterwards, the change of ionic conductivity of the film under the conditions of 60 DEG C is weighed.

The detection method reference standard of ionic conductivity is national standard:GT/T 20042.3-2009.

Solvent resistance is mainly weighed by film in polar non-solute dissolubility.Specifically method of testing is: Under room temperature condition, the corresponding membrane materials of 500mg are separately immersed in polar non-solute (10mL), will be corresponding after 60 days Membrane material takes out, and cleans (solvent for removing surface), then be dried in vacuo twice with deionized water, obtains the matter of corresponding membrane material Amount, and calculated weight loss late.

Test result indicates that with 6P2Exemplified by, the cross-linking type anion exchange membrane material for preparing of the present invention, at its 60 DEG C from Subconductivity rate 0.043S cm-1, the ionic conductivity after alkali process (10 days) is 0.040S cm-1, in solvent resistance test, Insoluble in DMAc, DMSO and NMP, rate of weight loss is respectively less than 5%.

For a further understanding of the present invention, a kind of gather with reference to embodiment to provided by the invention containing quaternary ammonium group Compound, anion-exchange membrane and preparation method thereof are illustrated, and protection scope of the present invention is not limited by the following examples.

XPY, X represents the polymer of variety classes (ratio of skeleton or comonomer different);Y=0, representative are that tertiary amine gathers Compound;Y=1, representative are using the quaternized corresponding polymer of iodomethane;Y=2, representative are to use (3- chloropropyls) trimethoxy Base silane (CPTMS) or the quaternized corresponding polymer of (3- chloropropyls) trimethoxy silane (CPTMS) system.

Shown in the structure such as formula (17) of specific raw material,

Wherein, x (CH3I)+y (CPTMS)=1,0 < n≤1, m=0,1 or 4;

1P0:N=0.1, m=1;1P1:N=0.1, m=1, x (CH3I)=1;1P2:N=0.1, m=1, y (CPTMS)= 1;

2P0:N=0.5, m=1;2P1:N=0.5, m=1, x (CH3I)=1;2P2:N=0.5, m=1, y (CPTMS)= 1;

3P0:N=1, m=1;3P1:N=1, m=1, x (CH3I)=1;3P2:N=1, m=1, y (CPTMS)=1;

4P0:N=0.1, m=0;4P1:N=0.1, m=0, x (CH3I)=1;4P2:N=0.1, m=0, y (CPTMS)= 1;

5P0:N=0.1, m=4;5P1:N=0.1, m=4, x (CH3I)=1;5P2:N=0.1, m=4, y (CPTMS)= 1。

Shown in structure such as formula (18)~formula (20) of specific raw material,

Wherein, x (CH3I)+y (CPTMS)=1.4,0 < n≤1;

6P0:N=0.7;6P1:N=0.1, x (CH3I)=1.4;6P2:N=0.7, x (CH3I)=0.4, y (CPTMS)= 1.0;

Wherein, x (CH3I)+y (CPTMS)=1.2,0 < n≤1;

7P0:N=0.6;7P1:N=0.6, x (CH3I)=1.2;7P2:N=0.6, x (CH3I)=0.2, y (CPTMS)= 1.0;

Wherein, x (CH3I)+y (CPTMS)=1.2,0 < n≤1;

8P0:N=0.6;8P1:N=0.6, x (CH3I)=1.2;8P2:N=0.6, x (CH3I)=0.2, y (CPTMS)= 1.0。

Tertiary amine polymer P0Preparation

The polymer such as the polyether sulphone, poly aryl ether ketone that side chain contains tertiary amine group are used as raw material.Its preparation process is shown in Document:Journal of Membrane Science 354(2010)23-31;Polymer 51(2010)5407-5416; Macromolecules 42(2009)8711-8717;Journal of Membrane Science 415-416(2012) 205-212;J.Mater.Chem.,2012,22,22706-22712;J.Appl.Polym.Sci.,2013DOI:10.1002/ app.37523。

Embodiment 1

Polymer 1P1Preparation process

Under nitrogen protection, by 7.00 grams of (12.0mmol) tertiary amine-type polymer 1P0It is dissolved in the N, N- of the drying of 115mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.71 grams (12.0mmol) is added thereto.Room temperature reaction After 24h, above-mentioned reaction solution is film-made using the method for casting film-forming in 60 DEG C of baking ovens, after vaporing away most of solvent, then (120 DEG C) vacuum drying are heated except the solvent remained in striping, to be cooled to room temperature, finally give thin polymer film.Will Then film soaks 48h, and carry out three times respectively at soaking 48h progress ion exchanges in 1M sodium hydroxide solutions in deionized water Solution cleaning above.Finally, film is preserved in deionized water, it is stand-by.

Embodiment 2

1P2Preparation process

Under nitrogen protection, by 7.00 grams of (12.0mmol) tertiary amine-type polymer Ps0It is dissolved in the N, N- of the drying of 115mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 2.37 grams (12.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount [its dosage is CPTMS 0.5% (molar equivalent)].Temperature control 85 DEG C, after reacting 24h, 5mL 95%EtOH are added, continue to react (hydrolysis) 30 minutes.Casting film-forming is used in 60 DEG C of baking ovens Method above-mentioned reaction solution is film-made, after vaporing away most of solvent, then heated (120 DEG C) vacuum drying with except striping The solvent of interior residual, is cooled to room temperature, finally gives thin polymer film.By film respectively at soaking 48h in 1M sodium hydroxide solutions Ion exchange is carried out, then soaks 48h in deionized water, and carries out the solution cleaning more than three times.Finally, film is stored in It is stand-by in ionized water.

1P prepared by Examples 1 and 21With 1P2The carry out performance test of film, for test result referring to table 1, table 1 is 1P1With 1P2The performance control of film.

The 1P of table 11With 1P2The performance control of film

Referring to Fig. 1, Fig. 1 is anion-exchange membrane 1P of the present invention1And 1P2Structure and polymeric quartenary ammonium procedure chart.

Referring to Fig. 2, Fig. 2 is polymer 1P in the present invention0(left side) and cross-linked polymer 1P2The photoelectron spectroscopy control on (right side) Figure.

Referring to Fig. 3, Fig. 3 is cross-linked polymer 1P in the present invention2Solid23Si NMR spectras.

Referring to Fig. 4, Fig. 4 is polymer 1P in the present invention1With cross-linked polymer 1P2INFRARED SPECTRUM compares figure.

Referring to Fig. 5, Fig. 5 is cross-linked polymer 1P under room temperature condition2(60 days) are soaked in DMAc (a), DMSO (b) and NMP (c) pictorial diagram in.

Referring to Fig. 6, Fig. 6 is linear polymer 1P in the present invention1With cross-linked polymer 1P2Alkaline stability compares figure.

Referring to Fig. 7, Fig. 7 is that solid state nmr tests cross-linked polymer 1P2Alkaline stability figure.

Referring to Fig. 8, Fig. 8 is linear polymer 1P1With cross-linked polymer 1P2Ionic conductivity changes compares figure after alkali process.

Embodiment 3

2P1Preparation process

Under nitrogen protection, by 6.01 grams of (10.0mmol) tertiary amine-type polymer 2P0It is dissolved in the N, N- of the drying of 100mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.42 grams (10.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 4

2P2Preparation process

Under nitrogen protection, by 6.01 grams of (10.0mmol) tertiary amine-type polymer 2P0It is dissolved in the N, N- of the drying of 100mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.Other operating procedures are the same as embodiment 2.

Embodiment 5

3P1Preparation process

Under nitrogen protection, by 6.17 grams of (10.0mmol) tertiary amine-type polymer 3P0It is dissolved in the N, N- of the drying of 102mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.42 grams (10.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 6

3P2Preparation process

Under nitrogen protection, by 6.17 grams of (10.0mmol) tertiary amine-type polymer 3P0It is dissolved in the N, N- of the drying of 102mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.Other operating procedures are the same as embodiment 2.

Embodiment 7

4P1Preparation process

Under nitrogen protection, by 5.70 grams of (10.0mmol) tertiary amine-type polymer 4P0It is dissolved in the N, N- of the drying of 96mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.42 grams (10.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 8

4P2Preparation process

Under nitrogen protection, by 5.70 grams of (10.0mmol) tertiary amine-type polymer 4P0It is dissolved in the N, N- of the drying of 96mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.Other operating procedures are the same as embodiment 2.

Embodiment 9

5P1Preparation process

Under nitrogen protection, by 6.26 grams of (10.0mmol) tertiary amine-type polymer 5P0It is dissolved in the N, N- of the drying of 103mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.42 grams (10.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 10

5P2Preparation process

Under nitrogen protection, by 6.26 grams of (10.0mmol) tertiary amine-type polymer 5P0It is dissolved in the N, N- of the drying of 103mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.Other operating procedures are the same as embodiment 2.

Embodiment 11

6P1Preparation process

Under nitrogen protection, by 5.16 grams of (10.0mmol) tertiary amine-type polymer 6P0It is dissolved in the N, N- of the drying of 90mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.99 grams (14.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 12

6P2Preparation process

Under nitrogen protection, by 5.16 grams of (10.0mmol) tertiary amine-type polymer 6P0It is dissolved in the N, N- of the drying of 90mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.85 DEG C of temperature control, after reacting 24h, recover to room temperature, to reaction System adds the iodomethane of 0.568 gram (4.0mmol), and room temperature continues to react 24h.Other operating procedures are the same as embodiment 2.

Embodiment 13

7P1Preparation process

Under nitrogen protection, by 4.65 grams of (10.0mmol) tertiary amine-type polymer 7P0It is dissolved in the N, N- of the drying of 83mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.71 grams (12.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 14

7P2Preparation process

Under nitrogen protection, by 4.65 grams of (10.0mmol) tertiary amine-type polymer 7P0It is dissolved in the N, N- of the drying of 83mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.85 DEG C of temperature control, after reacting 24h, recover to room temperature, to reaction System adds the iodomethane of 0.284 gram (2.0mmol), and room temperature continues to react 24h.Other operating procedures are the same as embodiment 2.

Embodiment 15

8P1Preparation process

Under nitrogen protection, by 4.55 grams of (10.0mmol) tertiary amine-type polymer 8P0It is dissolved in the N, N- of the drying of 80mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, the iodomethane of 1.71 grams (12.0mmol) is added thereto.Other operation steps Suddenly with embodiment 1.

Embodiment 16

8P2Preparation process

Under nitrogen protection, by 4.55 grams of (10.0mmol) tertiary amine-type polymer 8P0It is dissolved in the N, N- of the drying of 80mL milliliters In dimethyl acetamide, after dissolving completely to be mixed, (3- chloropropyls) trimethoxy of 1.99 grams (10.0mmol) is added thereto The anhydrous KI of base silane (CPTMS) and catalytic amount.85 DEG C of temperature control, after reacting 24h, recover to room temperature, to reaction System adds the iodomethane of 0.284 gram (2.0mmol), and room temperature continues to react 24h.Other operating procedures are the same as embodiment 2.

Alkali stability experiment is carried out to anion-exchange membrane prepared by embodiment 1~16 respectively and solvent resistance is surveyed Examination, referring to table 2, table 2 is alkaline stability and the solvent resistance control of anion-exchange membrane prepared by embodiment 1~16.

Alkaline stability and the solvent resistance control of anion-exchange membrane prepared by the embodiment 1~16 of table 2

As shown in Table 2, the cross-linking type anion exchange membrane material that prepared by the present invention has higher alkaline stability and resistance to Solvent borne.

A kind of polymer containing quaternary ammonium group provided by the invention, anion-exchange membrane and preparation method thereof are entered above Detailed introduction is gone, specific case used herein is set forth to the principle and embodiment of the present invention, and the above is real The explanation for applying example is only intended to help the method and its core concept for understanding the present invention, it is noted that for the art For those of ordinary skill, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, These are improved and modification is also fallen into the protection domain of the claims in the present invention.

Claims (8)

  1. A kind of 1. polymer containing quaternary ammonium group, it is characterised in that by side chain contain the polymer of tertiary amine group with it is quaternized Obtained after reagent reacting;
    The polymer that the side chain contains tertiary amine group is side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine group PAEK and side chain contain one or more in tertiary amine group poly (aryl ether sulfone ketone);
    The quaternizing agent is iodomethane and (3- chloropropyls) trimethoxy silane, (3- chloropropyls) trimethoxy silane, iodine Methane and (3- chloropropyls) trimethoxy silane system or (3- chloropropyls) trimethoxy silane system;
    (3- chloropropyls) the trimethoxy silane system is (3- chloropropyls) trimethoxy silane and iodo thing;The iodo thing For anhydrous sodium iodide and/or anhydrous KI.
  2. 2. polymer according to claim 1, it is characterised in that the side chain contains in the polymer of tertiary amine group, institute State and be connected between tertiary amine group and main chain by alkyl group;
    The alkyl group includes-CH2-、-CH2CH2-、-CH2CH2CH2- and-CH2(CH2)4CH2- in one or more.
  3. A kind of 3. preparation method of anion-exchange membrane, it is characterised in that comprise the following steps,
    A) under protective atmosphere, the polymer, quaternizing agent and anhydrous polar aprotic that side chain is contained to tertiary amine group are molten After agent hybrid reaction, the polymer solution containing quaternary ammonium group is obtained;
    The polymer that the side chain contains tertiary amine group is side chain contains the polyether sulphone of tertiary amine group, side chain contains tertiary amine group PAEK and side chain contain one or more in tertiary amine group poly (aryl ether sulfone ketone);The quaternizing agent be iodomethane and (3- chloropropyls) trimethoxy silane, (3- chloropropyls) trimethoxy silane, iodomethane and (3- chloropropyls) trimethoxy silane System or (3- chloropropyls) trimethoxy silane system;
    (3- chloropropyls) the trimethoxy silane system is (3- chloropropyls) trimethoxy silane and iodo thing;The iodo thing For anhydrous sodium iodide and/or anhydrous KI;
    B alcohols solvent) is added in the polymer solution containing quaternary ammonium group obtained to above-mentioned steps and carries out partial hydrolysis reaction Afterwards, casting solution is obtained;
    C the casting solution for) obtaining above-mentioned steps carries out casting film, while after carrying out self-crosslinking process, obtains anion exchange Film.
  4. 4. preparation method according to claim 3, it is characterised in that (3- chloropropyls) the trimethoxy silane system is (3- chloropropyls) trimethoxy silane and iodo thing;The iodo thing is anhydrous sodium iodide and/or anhydrous KI.
  5. 5. preparation method according to claim 3, it is characterised in that the molal quantity of the quaternizing agent is less than or equal to The side chain contains the molal quantity of tertiary amine group in the polymer of tertiary amine group.
  6. 6. preparation method according to claim 3, it is characterised in that the step A) in, the temperature of the reaction is 60 ~100 DEG C, the time of the reaction is 18~48 hours.
  7. 7. preparation method according to claim 3, it is characterised in that the time control of the partial hydrolysis reaction is polymerizeing Thing solution gel concentration is less than critical gel strength.
  8. 8. preparation method according to claim 3, it is characterised in that the temperature of the self-crosslinking process is 50~70 DEG C, The time of the self-crosslinking process is 8~12h.
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